Phénylhalogénohydrodigermanes

The symmetric and unsymmetric phenylchlorohydrodigermanes can be isolated or characterized via partial halogenation of the GeH bonds of the symmetrical phenylhydrodigermanes Ph 2 (H)GeGe(H) 2 Ph, Ph(H) 2 GeGe(H) 2 Ph by chloromethyl methyl ether and carbontetrachloride. Some of these phenylchlorohydrodigermanes are formed by insertion of phenylchlorogermylene (PhGeCl) on the GeH or GeCl bonds of the phenylchlorohydrogermanes. The hydrolysis of the monochloro phenylhydrodigermanes Ph 2 (Cl)GeGe(H) 2 and Ph(Cl)(H)GeGe(H) 2 Ph leads to the phenyl phenylhydrogermyl digermoxanes [Ph 2 (H)GeGePh 2 ] 2 O and [Ph(H) 2 GeGe(H)Ph] 2 O. Treatment of these oxides with the concentrated aqueous solutions of hydracides leads to the monofluorinated, brominated and iodinated phenylhydrodigermanes Ph 2 (H)GeGe(X)Ph 2 and Ph(H) 2 GeGe(H)(X)Ph (X) = F, Br, I). Phenylchlorohydrodigermanes decompose thermally by α‐elimination on one germanium atom with formation of germylene and phenylchlorohydrogermane. The physico‐chemical IR. and NMR. study of these phenylhalogenohydrodigermanes indicates that, if the vGeH frequency variations are mostly linked to the inductive effects of the substituents on the same germanium, the variations of the chemical shifts of the GeH protons seem to be due to many factors and especially to the inductive effect of the substituents on the germanium and the magnetic anisotropy of the GeX bonds.